N,n&#39;-dioleoyl-2,2&#39;-di-piperidylmethane



United States Patent 3,431,269 N,N-DIOLEOYL-2,2-DI-PIPERIDYLMETHANEEvald L. Skau, Robert R. Mod, and Frank C. Magne, New Orleans, La.,assignors to the United States of America as represented by theSecretary of Agriculture N0 Drawing. Continuation-impart of applicationSer. No. 361,925, Apr. 2, 1964. This application Sept. 20, 1965, Ser.No. 488,823

U.S. Cl. 260-294 Int. Cl. C07d 29/30; C08f 45/44 1 Claim ABSTRACT OF THEDISCLOSURE A nonexclusive, irrevocable, royalty-free license in theinvention herein described, throughout the world for all purposes of theUnited States Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

This application is a continuation-in-part of Ser. No. 361,925, filedApr. 2, 1964, now US. Patent No. 3,248,- 396, which was a division ofSer. No. 260,923, filed Feb. 25, 1963, now U.S. Patent No. 3,219,612.

This invention relates to certain compounds which are N-acyl derivativesof cyclic imines, to some unique mixtures of N-acyl derivatives ofcyclic imines, and to plastic compositions, the plasticizer component ofwhich is at least one of the compounds or one of the unique mixturesthat are the subject of this invention. More particularly, thisinvention relates to N,N-disubstitute*d long chain aliphatic amides theacyl component of which if saturated is an alkanoic acyl containing from10 to 18 carbon atoms, and if unsaturated is an alkenoic acyl containingfrom 18 to 22 carbon atoms, the amide nitrogen in all cases being amember of a heterocyclic ring or in the case of a fused ring system oneof the heterocyclic rings, all of the other ring members being carbon ornitrogen atoms.

This invention, in addition, relates to certain other new amideplasticizers wherein the acyl component is derived from dibasic alkanoicacids, from epoxidized alkanoic acids and from dimer acids.

This invention also relates to certain mixtures of the above-mentionedamides which individually or in combination with other mixtures ofamides are compatible plasticizers for vinyl chloride resins.

We have discovered that the compounds and the mixtures of compounds thatare the subject of this invention are good, compatible, solvent-typeplasticizers for vinyl chloride resins. Moreover, the compounds andmixtures of compounds that are the subject of this invention areetiicient primary solvent-type plasticizers which can be made from lowprice fatty acids and which exhibit good compatibility with and impartlow volatility loss, re-

3,431,269 Patented Mar. 4, 1969 sistance to microbial action, excellentlow temperature properties, and stability to northern light exposure topolymer and copolymer resins of vinyl chloride.

The terms vinyl type resin and vinyl chloride resin are used throughoutthis specification and claims to refer to polymers and copolymers ofmonomers containing vinyl chloride in a predominant proportion byweight. Terms such as compatible, good compatibility, and compatibleplasticizer in reference to the palsticizers which are the subject ofthis invention are used throughout the specification to refer toplasticizers that show no sign of exudation, migration to the surface,for at least two weeks when the plasticizers are present in the resin inproportions of about parts by weight of plasticizer to parts by weightof resin.

Not only are the compounds that are subject of this invention useful asplasticizers for vinyl chloride. resins, but they are also efficient,compatible softeners for Buna N rubber, imparting low volatility lossand excellent low temperature properties to the plasticized rubbercompositions. Buna N is a copolymer of butadiene 'with about 25%acrylonitrile. See Whitby et al., Synthetic Rubber, pages 794 and 795(John Wiley & Sons, Inc., New York, 1954).

If :a resin is plasticized with a compound with 'which it has onlylimited compatibility, the plasticizer soon exudes or migrates to thesurface unless the plasticizer is used either in a limited amount or isused in conjunction with a mutual solvent (a compatible auxiliaryplasticizer) to obtain adequate compatibility.

It is known in the art that compounds similar to those which are thesubject of this invention exhibit reasonably good compatibility forhydrophyllictype resins but in order to obtain adequate flexibility mustbe employed together with a secondary or an auxiliary plasticizer asseen for example United States Patent No. 2,339,056.

It would be expected from the recognized compatibility of compoundsrelated to the type herein described with polyvinyl acetals(hydrophyllic type resins), that these compounds would be quiteincompatible with polymers of the vinyl chloride type. We havediscovered, however, that not only are the particular compounds andcompound mixtures herein described compatible as primary plasticizerswith vinyl chloride resins but as we note above they are compatible withthe hydrophyllic type resins as well.

Not only are the particular compounds and mixtures of compounds hereindescribed compatible vinyl type resin plasticizers, but the instantinvention is considerably broader in that it also contemplates the useof the compatible (compatible with respect to the particular resininvolved) binary, ternary, or multiple component mixtures of N-acylcyclic imines of saturated, monounsaturated, and polyunsaturated acidssuch as can be derived from animal, fish, or vegetable fats and oilssuch as tallows, white greases, merihaden oil, cottonseed oil, sobeanoil, rapeseed oil, Crambe abyssinica seed oil, jojoba oil, parsley seedoil, Limnanthes douglasii seed oil, palm oil, Vernom'a anrhelminticaseed oil, castor oil, foots, or from tall oil acids or rosin acids, andother seed oils.

The N-acyl derivatives of this invention decrease in their degree ofcompatibility as the alkyl portion of the acyl group (if saturated)increases in chain length beyond 15 carbon atoms and they areincompatible when the chain length is 17 or more carbon atoms. Ingeneral, the

compatibility of a mixture of N-acyl cyclic imines containing aconsiderable proportion of these less compatible or incompatible N-acylcyclic imines can be improved by mixing with a compatible plasticizer orby reducing the proportion of the incompatible saturated constituent bysuch procedures as fractional distillation or fractional crystallizationeither before or after the amidation step in the preparation of theN-acyl cyclic imine mixture. Similarly, the N-acyl derivatives of thisinvention decrease in their degree of compatibility as the alkyl portionof the acyl group of the N-acyl derivative (if unsaturated) increases inunsaturation beyond monounsaturation. In general, the compatibility ofsuch a polyunsaturated derivative or of a mixture of N-acyl cyclicimines containing such polyunsaturated acyls can be increased by mixingwith a suitable amount of a compatible plasticizer or by decreasing thepolyuusaturation of some or all of the polyunsaturated constituentseither by physical means, such as fractionation, or by chemical meanssuch as selective hydrogenation, cyanoethylation, halogenation,epoxidation, forniylation, maleination, dimerization, cyclization, orthe like either before or after the amidation step in the preparation ofthe N-acyl imine or N-mixed acyl cyclic imine. The specific componentratio of compatible compositions can be established according to thescheme set forth in our US. Patent No. 3,219,664, for example.

Also included among the operable N-acyl cyclic imines are those whoseacyls are the acyls of the following groups of acids: alkanoic acidswith substituents in the chain such as dichloro stearic acid;acyloxyacids such as 12-acetoxyoleic, 12-acetoxystearic and9,10-diacetoxystearic acids and the like; 12-beta-cyanoethoxyoleic and12-cyanoethoxystearic acids and the like; ricinoleic acid;

phenylstearic acid; phenoxyacetic acid; mono-, di-, or tri-epoxy stearicacids; monoor diepoxy oleic acid; epoxydocosanoic acid; dimerized ortrimerizcd linolenic, linoleic or oleic acid, etc, cyclic acids such ascyclized linoleic and/or linolenic acids; Diels-Alder adducts of suchpolyenoic acids as tung oil acids or soybean acids, the Diels-A-lderadducts of tung oil acids with di-alkyl maleates, alkyl acrylates,acrylonitrile, fumaronitrile and the like; tall oil acids; and rosin orterpene-derivcd acids such as abietic, l-pimaric, pinonic, pinic and thegammalactone of beta-hydroxyisopropyl pimelic acid; as well as themono-alkyl esters of dibasic acids such as pinic, adipic, sebacic,brassylic, carboxystearic, phthalic, terephthalic and dialkylphosphonostearic acids, and the like.

Terms such as dimer acid, or dimerized acids are used indiscriminatelyto refer to acids or mixtures of acids consisting essentially of dibasicacids containing from 32 to 44 carbon atoms resulting from thepolymerization or dimerization of long chain C to C unsaturated fattyacids. Terms such as trimer acid, or trimerized acids are usedindiscriminately to refer to acids or mixtures of acids consistingessentially of tribasic acids containing from 48 to 66 carbon atomsresulting from the polymerization or trimerization of long chain C to Cunsaturated fatty acids.

Also anticipated are the N-acyl derivatives of the alkanol andpolyalkanol cyclic imines wherein the alkanol or polyalkanol group isesterified by the same or a different acyl group from that acylating theimino nitrogen resulting in N-acyl(acyloxyalkyl)piperidines such as1-oleoyl-4(3-acetoxypropyl)piperidine and the like.

The compounds of the instant invention were tested for vinylchloride-vinyl acetate (95-5) copolymer resin Vinylite (VYDR) and inpolyvinyl chloride (Geon 101) in a standard formulation comprising:63.5% of Vinylite VYDR or Geon 101, plasticizer, 0.5% stearic acid, and1.0% basic lead carbonate. Vinylite (VYDR) is a copolymer of about 94.5to 96.0% vinyl chloride with about 4.0 to 5.5% vinyl acetate, producedand marketed by the Union Carbide and Carbon Corporation. Geon 101 is apoly(vinyl chloride) homopolymer produced and marketed by the B. F.Goodrich Chemical Company.

The foregoing formulation for each sample was milled, molded, andtested. In all examples, the sample was rated as incompatible if themolded stock showed any evidence of exudation or migration to thesurface during a shelf storage of two weeks.

The compounds that are the subject of this invention are convenientlyprepared by reacting the appropriate imine, which in every case is acyclic imine wherein the nitrogen atom is a member of either the ring ora memoer of one of the rings if a fused ring compound is involved, withthe appropriate acid or corresponding acid chloride. In any event,methods for preparing compounds such as those herein described are wellknown to those skilled in the art of fatty acid chemistry. The detailsof individual preparations are listed in the operating examples whichfollow:

EXAMPLE 1 N-oleoylpiperidine.Twenty-two and four tenths grams (0.26mole) of piperidine were dissolved in 60 milliliters of benzene and 39.7grams (0.13 mole) of oleoyl chloride were added dropwise with stirring.After stirring for an additional hour, the reaction mixture wasfiltered, washed successively with dilute hydrochloric acid and water,and dried over anhydrous sodium sulfate. Free acid was removed bypercolating the benzene solution through a column of activated aluminaand eluting the amide with a 1:1 ethanol-benzene mixture. The solventwas then removed by stripping under reduced pressure. Analysis of theproduct, N-oleoylpiperidine: C, 78.15% (theory 78.95); H, 12.07% (theory12.40); N, 404% (theory 4.04).

EXAMPLE 2 N oleoylhexamethylenimine.N oleoylhexamethylenimine wasprepared by the procedure of Example 1 from 9.9 grams (0.10 mole) ofhexamethylenimine, 30.0 grams (0.10 mole) of oleoyl chloride, and 8grams (0.10 mole) of pyridine. Analysis of the product,N-oleoylhexamethylenirnine: C, 78.83% (theory 79.21); H, 12.11% (theory12.46); N, 3.79% (theory 3.85).

EXAMPLE 3 N-oleoyl-2-methylpiperidine.A mixture of 31.6 grams (0.32mole) of Z-methylpiperidine, 60 grams (0.21 mole) of oleic acid, and 20milliliters of benzene was refluxed in an apparatus equipped with aDean-Stark trap until the evolution of water ceased. The reactionmixture was diluted with milliliters of commercial hexane, washedsuccessively with dilute hydrochloric acid and Water, and dried overanhydrous sodium sulfate. Free acid was removed by percolating thehexane solution through a column of activated alumina, and eluting theamide with a 1:1 hexane-ethanol mixture. The solvent was removed bystripping under reduced presure. Analysis of the product,N-oleoyl-2-methylpiperidine: C, 78.87% (theory 79.20); H, 12.13% (theory12.47); N, 3.86% (theory 3.85).

EXAMPLE 4 N oleoyl 3-methylpiperidine.-Noleoyl-3-methylpiperidine wasprepared by the procedure of Example 3 from 31.6 grams (0.32 mole) of3-methylpiperidine, and 60 grams (0.21 mole) of oleic acid. Analysis ofthe product, N-oleoyl-3-methylpiperidine: C, 79.03% (theory 79.20); H,12.30% (theory 12.47); N, 3.89% (theory 3.85

EXAMPLE 5 N-oleoyl-4-methylpiperidine.N-oleoyl-4-methylpiperidine wasprepared by the procedure of Example 3 from 31.6 grams (0.32 mole) of4-methylpiperidine and 60 grams (0.21 mole) of oleic acid. Analysis ofthe product, N oleoyl 4 methylpiperidine: C, 78.80% (theory 79.20%); H,12.08% (theory 12.47); N, 3.86% (theory 3.85).

EXAMPLE 6 N oleoyl 4-ethylpiperidine.-N-oleoyl-4-ethylpiperidine wasprepared by the procedure of Example 3 from 14.4 grams (0.13 mole) of4-ethylpiperidine and 30 grams (0.11 mole) of oleic acid. Analysis ofthe product, N- oleoyl-4-ethylpiperidine: C, 79.17% (theory 79.45); H,12.62% (theory 12.45); N, 3.75% (theory 3.71).

EXAMPLE 7 N oleoyl-4-nonylpiperidine.-N-oleoyl-4-nonylpiperidine wasprepared by the procedure of Example 3 from 27 grams (0.13 mole) of4-nonylpiperidine and 30 grams (0.11 mole) of oleic acid. Analysis ofthe product, N- oleoyl-4-nonylpiperidine: C, 80.21% (theory 80.70); H,12.67% (theory 12.80); N, 2.95% (theory 2.90).

EXAMPLE 8 N oleoyl 2-methyl-S-ethylpiperidine.N-oleoyl-2-met-hyl-5-ethylpiperidine was prepared from 27 grams (0.21 mole) of2-methyl-S-ethylpiperidine and 40 grams (0.14 mole) of oleic acid byExample 3, except that toluene was used as the entraining solvent.Analysis of the product, N-oleoyl-2-methyl-5-ethylpiperidine: C, 79.51%(theory 79.66); H, 12.40% (theory 12.51); N, 3.79% (theory 3.85).

EXAMPLE 9 Piperidide of selectively hydrogenated cottonseed oil fattyacids.-The piperidide of selectively hydrogenated cottonseed oil fattyacids were prepared by the procedure of Example 3 from 18.6 grams (0.22mole) of piperidine and 40 grams (0.14 mole) of selectively hydrogenatedcottonseed oil fatty acids. (The selectively hydrogenated cottonseed oilfatty acids had an iodine value of 73.2, a thiocyanogen value of 68.0,and a neutralization equivalent of 274.) The product, the piperidides ofselectively hydrogenated cottonseed oil fatty acids, had a nitrogencontent of 4.08%.

EXAMIPLE 10 Piperidide of animal acids.-The piperidide of animal acids(Neofat No. 65) was prepared by the procedure of Example 3 from 18.6grams (0.22 mole) of piperidine and 40 grams (0.15 mole) of Neofat 65.(The animal acids consisted of a mixture of fatty acids having thefollowing composition: 2% rnyristic, 26% palmitic, 16% stearic, 48%oleic, and 8% linoleic acids.) The product, the piperidide of animalacids, had a nitrogen content of 3.95%.

EXAMPLE 11 N oleoylpyrrolidine.-N-oleoylpyrro1idine was prepared by theprocedure of Example 3 from 15.1 grams (0.21 mole) of pyrrolidine and 40grams (0.14 mole) of oleic acid. Analysis of the product,N-oleoylpyrrolidinez C, 77.81% (theory 78.67); H, 12.11% (theory 12.32);N, 4.30% (theory 4.17).

EXAMPLE 12 N oleoyl 1,2,3,4 tetrahydroquinoline.-N oleoyl-1,2,3,4-tetrahydroquinoline was prepared from 15 grams (0.11 mole) of1,2,3,4-tetrahydroquinoliue, 35 grams (0.11 mole) of oleoyl chloride,and 9.2 grams (0.11

- mole) of pyridine by the procedure of Example 1, except that the freeunreacted acid was removed by washing with 4% alcoholic KOH followed bywater washings. Analysis of the productN-oleoyl-1,2,3,44tetrahydroquinoline: C, 80.89% (theory 81.48); H,10.91% (theory 10.81); N, 3.31% (theory 3.52).

6 EXAMPLE 13 N oleoyl 2,6dimethylpiperidine.-N-oleoyl-2,6-dimethylpiperidine was prepared by theprocedure of Example 1 from 30.1 grams (0.27 mole) of2,6-dimethylpiperidine, and 40 grams (0.13 mole) of oleoyl chloride.Analysis of the product, N-oleoyl-2,6-dimethylpiperidine: C, 79.19%(theory 79.12); H, 12.43% (theory 12.30); N, 3.74% (theory 3.72).

EXAMPLE 14 EXAMPLE 15 N-oleoyl-S-azabicyclo[3,2,2]nonane was prepared bythe procedure of Example 12 from 12.5 grams (0.10 mole) of3-azabicyclo[3,2,2]nonane, 30 grams (0.10 mole) of oleoyl chloride, and8 grams (0.10 mole) of pyridine. Analysis of the product,n-oleoyl-3-azabicyclo [3.2.2]nonane C, 79.20% (theory 80.09); H, 11.95%(theory 12.06); N, 3.40% (theory 3.60).

EXAMPLE 16 N-palmitoylpiperidine.-N-palmitoylpiperidine was prepared bythe procedure of Example 3 from 19 grams (0.22 mole) of piperidine and40 grams (0.15 mole) of palmitic acid. Analysis of the product,N-palmitoylpiperidine: C, 78.02% (theory 77.88); H, 12.70% (theory12.77); N, 3.89% (theory 4.33).

EXAMPLE 17 N,N'-sebacoyldipiperidine.-N,N'-sebacoyldipiperidine wasprepared by the procedure of Example 3 from 78 grams (0.92 mole) ofpiperidine and 40 grams (0.20 mole) of sebacic acid, except that thefree unreacted acid was removed by dissolving the reaction product incarbon tetrachloride, treating with a slight excess of 4% alcoholic KOH,and washing with water. Analysis of the product,N,N-sebacoyldipiperidine: C, 71.35% (theory 71.31); H, 10.63% (theory10.70); N, 8.18% (theory 8.32).

EXAMPLE 18 N stearoylpiperidine.N-stearoylpiperidine was prepared by theprocedure of Example 3 from 27 grams (0.32 mole) of piperidine and 45grams (0.16 mole) of stearic acid. Analysis of the product,N-stearoylpiperidine: C, 78.50% (theory 78.49); H, 12.75% (theory12.90); N, 3.96% (theory 3.98).

EXAMPLE l9 Dipiperidide of dimer acid (Empol 1014).-The dipiperidide ofdimer acid was prepared by the procedure of Example 3 from 18.3 grams(0.22 mole) of piperidine and 40 grams (0.07 mole) of dimer acid (Empol1014). The product, the dipiperidide of dimer acid, had a nitrogencontent of 3.98%.

EXAMPLE 20 Mixed piperidides of oleic acid-This was a physical mixtureconsisting of 3.6% by weight of the sample of Example 3, 46.4% by weightof the sample of Example 4,

7 35.7% by weight of the Sample of Example 5, and 14.3% of the sample ofExample 13.

EXAMPLE 21 N-erucoylpiperidine.--N-erucoylpiperidine was prepared by theprocedure of Example 3 from 11.1 grams (0.13) mole) of piperidine and 40grams (0.12 mole) of erucic acid. Analysis of the product,N-erucoylpiperidine: C, 79.84% (theory 7986); H, 12.61% (theory 12.67);N, 3.48% (theory 3.41).

EXAMPLE 22 N-decanoyl-4-nonylpiperidine.N-decanoyl-4-nonylpiperidine wasprepared by the procedure of Example 3 from 53 grams (0.25 mole) of4-nonylpiperidine and 40 grams (0.23 mole) of decanoic acid. Analysis ofthe product, N-decanoyl-4-nonylpiperidine: C, 78.69% (theory 78.78) H,12.90% (theory 12.96); N, 3.76% (theory 3.83).

EXAMPLE 23 N-epoxystearoylpiperidine.-N-epoxystearoylpiperidine wasprepared by epoxidation of N-oleoylpiperidine using perbenzoic acid. Theproduct, N-epoxystearoylpiperidine had an oxirane oxygen content of4.49%.

EXAMPLE 24 Piperidide of rapeseed oil fatty acids.-The piperidide ofrapeseed oil fatty acids was prepared by the procedure of Example 3 from18.5 grams (0.22 mole) of piperidine and 60 grams (0.20 mole) ofrapeseed oil fatty acids. The product, the piperidide of rapeseed oilfatty acids, had a nitrogen content of 3.56%.

EXAMPLE 25 N,N-dioleoyl-2,2'-dipiperidylmethane.-N,N'-dioleoyl-2,2-dipiperidylmethane was prepared by the procedure of Example 3 from18.1 grams (0.10 mole) of 2,2- dipiperidylmethane and 50 grams (0.18mole) of oleic acid. Analysis of the product,N,N'-dioleoyl-2,2-dipiperidylmethane: C, 78.52% (theory 79.30); H,12.14% (theory 12.19); N, 3.94% (theory 3.94).

EXAMPLE 26 N-oleoyl 4(5-nonyl) piperidine.-N-oleoyl-4(5-nony1)-piperidine was prepared by the procedure of Example 3 from 41.1 grams(0.19 mole) of 4-(5-nonyl(piperidine and 50 grams (0.18 mole) of oleicacid. Analysis of the product, N-oleoyl 4(5 nonyl)piperidine: C, 80.62%(theory 80.70); H, 12.80% (theory 12.80); N, 2.99% (theory 2.90).

EXAMPLE 27 Mixed piperidides of oleic acid.Mixed piperidides of oleicacid was prepared by the procedure of Example 3 from 55 grams (0.42mole) of mixed piperidines (commercial by-product mixture of alkylpiperidines) and 100 grams (0.35 mole) of oleic acid. The product, themixed piperidides of oleic acid, had a nitrogen content of 3.63%.

EXAMPLE 28 N,N'-dioleoylpiperazine.N,N'-dioleoylpiperazine was preparedby the procedure of Example 3 from 9.2 grams (0.11 mole) of piperazineand 60 grams (0.21 mole) of oleic acid. Analysis of the product,N,N'-diole0ylpiperazine: C, 77.77% (theory 78.04); H, 12.12% (theory12.13); N. 4.64% (theory 4.55).

EXAMPLE 29 N-oleoyl-N'-methylpiperazine.-N-oleoyl-N'-methylpiperazinewas prepared by the procedure of Example 1 from 23.3 grams (0.23 mole)of N-methylpiperazine and 35.0 grams (0.12 mole) of oleoyl chloride.Analysis of the product, N-oleoyl-N-methylpiperazine: C, 74.46% (theory75.70); H, 11.63% (theory 12.07); N, 7.43% (theory 7.68).

EXAMPLE 30 N,N-didecanoylpiperazine.--N,N'-didecanoylpiperazine wasprepared by the procedure of Example 17 from 13.8 grams (0.16 mole) ofpiperazine and 60.2 grams (0.35 mole) of decanoic acid. Analysis of theproduct, N,N-didecanoylpiperazine: C, 73.15% (theory 73.09); H, 11.68%(theory 11.75); N, 7.07% (theory 7.09).

EXAMPLE 31 Piperidide of cottonseed oil fatty acids.The piperidine ofcottonseed oil fatty acids was prepared by the procedure of Example 3from 18.6 grams (0.22 mole) of piperidine and 40 grams (0.14 mole) ofcottonseed oil fatty acids. The product, the piperidide of cottonseedoil fatty acids, had a nitrogen content of 3.94%.

EXAMPLE 32 N-linoleoylpiperidine.N-linoleoylpiperidine was prepared bythe procedure of Example 3 from 20 grams (0.23 mole) of piperidine and60 grams (0.21 mole) of linoleic acid. Analysis of the product,N-linoleoylpiperidine: C, 79.00% (theory 79.40); H, 11.77% (theory11.89); N, 3.92% (theory 4.03).

The samples of Examples 1 to 36, inclusive, were evaluated asplasticizers for Vinylite VYDR resin and the samples of Examples 1 and16 were evaluated as plasticizers for Geon 101 using the aforedescribedformulations. The results are reported in Table I which includes theresults for di-2-ethylhexylphthalate (DOP) as control.

The samples of Examples 1, 9, and 27 were evaluated as nitrile rubber(Hycar 1042-33% acrylonitrile) softeners. As also shown by Whitby, etal., on page 795, Hycar 1042 is an oil-resistant copolymer of butadienewith 33% acrylonitrile, manufactured and sold by the B. F. GoodrichChemical Company. The formulation employed was as follows:

These compositions were cured for 30 minutes at 310 F. None showed anysigns of exudation in 15 days. The evaluation results are given in TableII which also includes the results for the control, dibutylsebacate(DBS).

TABLE I Example Tensile 100% Elongation, Brittle Volatility Compat- No.Plasticizcr strength, modulus, percent point, loss, ibility 1 p.s.i.p.s.i. 0. percent 1 N-oleoylpiper'idine- 2, 670 1, 170 390 47 1.. do 22, 990 1, 400 330 41 Noleoylhexamethylennnme. 2, 650 1, 300 350 49 Noleyl-2-methylpiperidine. 2, 470 1, 240 310 39 0. 83N-oleoyl-3-methylpiperidine. 2, 500 1, 170 330 43 0. 79 Noleoyl-4-methylpiperidine. 2, 520 1, 240 310 -43 0. 65 Noleoyl-4-ethylpiperidine- 2, 760 1, 280 390 45 0. 47N-oleoyl-l-nonylpiperidine. 2, 780 1, 700 330 5 0. 27N-oleoyl-2-methyl-5-ethylpiperidine 2, 870 1, 340 380 37 0. 40Piperidide of hydrogenated cottonseed oil fatty acids.- 2, 660 1, 220370 45 0.38 Piperidide of animal acids 3 2, 710 1, 180 370 39 0. 88N-oleoylpyrrolidine 90 N-oleoyl-l,2,3,4-tetrahydroquinoline.N-oleoy1-2,fi-dimethylpiperidine. N oleoylcarbazole N,N-sebacoyldipiperidine- N stearoylpiperidine.

Dipiperidide of dimer acid (E Mixed piperidides of oleic acid 4N-erucoylpiperidine.

N-decanoylA-nonlypi 2, 880 1, 350 390 N -epoxystearoylpiperidine 2,8101, 180 340 Piperiddide of rapeseed oil fatty aci 2, 750 l, 300 340N,N-dioleoyl-2,2-dipiperidylmethane 2, 840 1, 190 390 N oleoyM(5-nonyl)pipe1'idine r 2, 990 1, 750 340 Mixed piperidides of oleic acid5 2, 910 1,380 370 N ,N-dioleoylpiperazine 2, 880 1, 330 380 N -oleoyl-N-methylpiperazine. 2, 510 1, 810 280 N,N -didecanoylpip erazine 2, 8301, 770 250 Piperidide of cottonseed oil fatty ac1 s. 2, 560 1, 200 330N-Linoleoylpiperidine Pipcridide of mixed acids GOOOC O OOOOOOOOO OOOOOOOOOOOOOOOOOO 34 Piperidide of mixed acids 35 Piperidide of mixed acids36 Pipcridlde of mixed acids 9 Di-2-ethylhexylphthalate (control) 3, 0501, 690 330 l C =Compatible, I=Incompatible.

2 Using poly(vinyl chloride) homopolymcr instead of Vinylite VYDR resin.

3 2% myristic acid, 26% palmitic acid, 16% stearic acid, 48% oleic acid,and 8% linolelc acid.

4 Mixture of 3.6%, 46.4%, 35.7%, and 14.3% by welght of samples ofExamples 3, 4, 5, and 13, respectively. 5 Made from a commercialby-product mixture of alkyl piperidines.

I! Mixture of 60% and 40% by Weight of the samples of Examples 16 and32, respectively.

7 Mixture of 32.5%, 32.5%, and 35.0% by weight of the samples ofExamples 1, 16, and 32, respectively. Mixture of 30% 30%, and 40% byweight of the samples of Examples 1, 16, and 32, respectively.

9 Mixture of 27.5 27.5%, and by Weight of the samples of Examples 1, 16,and 32, respectively.

TABLE II 300% modulus, p.s.i. Tensile strength, p.s.l. Ultimateelongation, Example N 0. percent Hardness, Brittle point, Volatibility,Swelling,

Shore A 0. percent percent Unaged Aged Unaged Aged Unaged Aged Samplesof vinylite VYDR resin plasticized with the 50 The soapy waterextractability can be reduced by the N-oleoylpiperidine of Example 1,the N-oleoyl-Z-methyluse of additives such as hydrocarbon extenders.piperidine of Example 3, the mixed piperidides of oleic We claim: acidof Example 20, and the N-oleoyl-Z,6-dimcthylpiper- 1.N,N-dioleoyl-2,2'di-piperidylmethane. idine of Example 13, respectively,were subjected to standard soil-burial tests using similar samples ofVYDR resin 5 References Cited glastiizizecllwiith N-olecgylimonilholtineas cizonttrols. After-b UNITED STATES PATENTS ays oca ize areas 0 lSCOcm 1011 in ma mg micro 1a attack appeared in the control. None of theother speci- 3,277,101 10/1966 Surrey 260 294'7 mens showed any signs ofdiscoloration after 56 days. OTHER REFERENCES After 85 days the samplesplasticized with N-oleoylpiperl idine, and N-oleoyl-2-methylpiperidinewere completely 2; et Trav' Chlm" v0 1395 to discolored, the sampleplasticized with the mixed piperidides of oleic acid showed onlylocalized discolonation, NORMA MILESTONE Primary Examiner and the sampleplasticized with N-oleoyl-2,6-dimethylpiperidine showed no signs ofdiscoloration. SPEVACK Assistant Examiner- Improved light stability andthermal stability can be U S c1 XR attained by inclusion of suitablestabilizers and/or antioxidants in the resin-plasticizer formulation.26030.2, 23, 32.6, 23.7, 294.7, 289, 239, 326.5, 315, 268

